Compositions comprising modified polysaccharides and uses thereof

ABSTRACT

Cationic and silicon substituents are introduced into polysaccharides thereby producing modified polysaccharides cationically substituted by quaternary ammonium groups and having a charge density of about 0.1 to about 2.5 meq/g, and further substituted by siliconate groups such that the modified polysaccharide has a silicon content of about 300 to about 5000 ppm. The modified polysaccharides have application in industrial, home care and personal care surface modifying formulations.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention is directed towards modified polysaccharides. Moreparticularly, the present invention is directed towards modifiedpolysaccharides having both cationic and organo-functional silaneconstituents, as well as surface modifying compositions containing suchmodified polysaccharides.

Water soluble polysaccharides find broad industrial application asrheology modifiers, film formers and binders. They are widely used asthickeners to control the rheology of various water-based formulations,such as latex paints, drilling muds, cosmetics, detergents and buildingmaterials. Natural polysaccharides such as cellulose, guar and starchare a large class of commercial water soluble polymers. Commoncommercially available chemically modified natural polysaccharidesinclude compounds such as Polyquaternium-10 (cationically modifiedhydroxyethylcellulose) and guar hydroxypropyltrimonium chloride(cationically modified guar gum). Such polysaccharides are often used insurface modifying compositions.

Surface modifying compositions containing various combinations ofsurfactants, conditioning agents and carriers are known. Such surfacemodifying compositions have application in a wide variety of uses,including industrial, household products, and personal care. Theseproducts typically comprise an anionic surfactant in combination with aconditioning agent such as a cationic conditioning polymer, a silicone,a hydrocarbon oil, a fatty ester, or combinations thereof.

Cationic conditioning polymers can act as conditioning and surfacemodifying agents in surface modifying compositions. These polymericconditioners help the substrate to which they are applied look and feelbetter by improving the physical condition of these surfaces (hence, thename “conditioning” in that they improve the surface of a substrate).For example, when the substrate is keratin or hair, the conditioner canmake dry hair feel smoother, shinier and more manageable. When thesubstrate is skin, cationic conditioners can serve a variety offunctions such as moisturizing and protection from the environment. Whenthe substrate is wood or other cellulosic material such as paper, theconditioners can aid in protecting or preserving the material. Examplesof substrates onto which compositions containing cationic conditioningpolymers can be applied include hair, skin, nails, keratin containingsubstrate, hard surface, carpet, fabric, leather, wood, plasticcontaining composition, and vinyl.

Among the ways in which some of these conditioning polymers work isthrough substantivity onto the substrate. Cationic conditioning polymersachieve substantivity to the substrate through a cationic charge thatpromotes binding to the innate anionic charge of the substrate to whichit is applied. Depending on the nature of the substrate, substantivityof the polymer onto the substrate can provide a film or barrierfunction. Other benefits include enhanced deposition of ingredients andimproved feel. Such ingredients can include silicone.

Silicones, or more precisely polysiloxanes, consist of an inorganicsilicon-oxygen backbone chain ( . . . —Si—O—Si—O—Si—O— . . . ) withorganic side groups attached thereto and have the general formula[R₂SiO]_(n) wherein R is an organic group such as methyl, ethyl orphenyl. The most common siloxane is polydimethylsiloxane (a/k/a PDMS orDimethicone), a clear silicone oil. Silicones present in surfacemodifying compositions, like cationic conditioning polymers, can alsoserve a variety of functions, including acting as a defoamers andimproving the feel and appearance of a substrate, making it smoother andshinier. However, silicones can be incompatible with typical surfacemodifying compositions, and tend to separate due to their low specificgravity.

In leave-on formulations such as wax emulsions, one function of cationicpolymers in the formulations is film forming (i.e., providing aprotective coating). Such wax emulsions are useful in a variety ofapplications, including paints/lacquers, printing inks, textiles, floorpolishes, wood and timber protection, automobile polishes, and paper andboard coatings.

In rinse-off formulations containing silicones, one function of cationicpolymers in the formulations is to aid in deposition of ingredients suchas silicone onto the substrate to which it is applied. Polyquaternium-10is an example of a common conditioning polymer used to aid in depositionof silicone onto the surface of the substrate (e.g., hair, skin or otheranionically-charged surfaces).

Unfortunately, once deposited silicone can be difficult to remove. Thisdeposition results in buildup with each consecutive application. Whenapplied by shampooing, such buildup can reduce the volume of the desiredhair style, resulting in a ‘droopy’ and flat hair style.

Attempted solutions to avoiding buildup have included treating the hairwith water-in-water emulsions containing cationic polymers with solublesalts in surfactant compositions. Clarifying shampoos can also be used;however, use of these shampoos on colored hair can cause the hair colorto fade faster. Low viscosity microemulsified silicone oils can becombined with cationic polymers; however, these are less effective fordifficult to manage hair. Accordingly, there remains a need forsilicone-containing surface modifying compositions that provide thebenefits of silicone without its associated problems such as buildup.

BRIEF SUMMARY OF THE INVENTION

Provided herein is a modified polysaccharide having both cationic andsilicon substituents. This modified polysaccharide is cationicallysubstituted with quaternary ammonium groups and has a charge density ofabout 0.1 to about 2.5 meq/g. More preferably, the polysaccharidesubstituted by quaternary ammonium groups has a charge density of about0.2 to about 2.0 meq/g. Even more preferably, the polysaccharidesubstituted by quaternary ammonium groups has a charge density of about0.8 to about 1.5 meq/g.

Quaternary ammonium groups useful in the modified polysaccharide arederived from a quaternary ammonium compound according to one of thegeneral formulae (I) or (II):

wherein

-   -   n is an integer from 1 to 16, preferably 1;    -   X is halogen, particularly fluorine, chlorine, bromine or        iodine, and preferably chlorine;    -   Z⁻ is an anion which may be inorganic, for example, halide        (fluoride, chloride, bromide or iodide, preferably chloride),        nitrate, nitrite; phosphate or hydroxide, or organic, for        example carboxylate such as acetate or propionate;    -   R is hydrogen or methyl, preferably hydrogen;    -   R¹, R² and R³, which may be the same or different, are each an        organic radical, preferably containing up to 10 carbon atoms,        with R¹, R² and R³ each preferably methyl.        Preferably, the quaternary ammonium compound is        glycidyltrimethylammonium chloride or its equivalent.

The modified polysaccharide is also substituted with siliconate groups,resulting in a modified polysaccharide having a silicon content of about300 to about 5000 ppm. Preferably, the ratio of cationic substituents tosilicon substituents on the polysaccharide is from about 1500:1 to about1:3. In a preferred embodiment, the silicon substituent is an alkylsilanol, more preferably methyl silanol.

In one embodiment the modified polysaccharide described herein canfurther be crosslinked to reduce its solubility in water.

An example of a suitable polysaccharide useful for modificationaccording to the present invention is a polygalactomannan. Usefulpolygalactomannans include fenugreek gum, guar gum, tara gum, locustbean gum and cassia gum. In one embodiment, the polygalactomannan isguar gum. In another embodiment, the polygalactomannan is tara gum.

Modified polysaccharides described herein have application inindustrial, home care and personal care surface modifying or cleansingformulations. For example, a surface modifying composition according tothe present invention can comprise from about 0.1 wt % to about 1.0 wt %by weight of the composition of a cationically modified and siliconegrafted polysaccharide; from about 5 wt % to about 60 wt % by weight ofthe composition of at least one surfactant; and a carrier.

In one embodiment, the cationically modified and silicone graftedpolysaccharide used in the surface modifying composition is acationically modified and silicone grafted polygalactomannan. Examplesof base polygalactomannans useful forming the modified polysaccharideused in the surface modifying composition include fenugreek gum, guargum, tara gum, locust bean gum, cassia gum and combinations thereof. Ina preferred embodiment, the polygalactomannan is guar gum.

In another embodiment, the cationically modified and silicone graftedpolysaccharide used in the surface modifying composition is acationically modified and silicone grafted starch. Starches and floursuseful in the present invention can be chosen from any native source.Native sources include banana, corn, pea, potato, sweet potato, barley,wheat, rice, sago, amaranth, tapioca, sorghum, waxy maize, waxy rice,waxy barley, waxy potato, waxy sorghum, starches containing highamylose, and the like. Preferred starches are low amylose or waxystarches, including waxy maize, waxy rice, waxy potato, waxy sorghum,waxy cassava and waxy barley. Unless specifically distinguished,references to starch in this description are meant to include theircorresponding flours. References to starch are also meant to includestarch containing protein, whether the protein is endogenous protein orprotein added from an animal or plant source such as zein, albumin, andsoy protein.

Surface modifying compositions according to the present invention canuse a variety of one or more surfactants. Such surfactants includeanionic surfactants, cationic surfactants, non-ionic surfactants,amphoteric surfactants and combinations thereof.

The present invention further provides a method of achieving a modifiedsubstrate wherein the surface modifying composition described above isapplied to the substrate. Such substrates can vary depending upon thetype of surface modifying composition used (e.g., industrial, home careor personal care). For example, when the surface modifying compositionis a personal care composition, the substrate can be a keratinaceoussurface (e.g., hair, nail or skin). When the surface modifyingcomposition is a film forming composition, the substrate can be wood,cellulose, ceramic, glass, metallic or any other anionically chargedmaterial.

DETAILED DESCRIPTION OF THE INVENTION

As used herein “consumer product” means baby care, beauty care, fabric &home care, family care, feminine care, health care, products or devicesgenerally intended to be used or consumed in the form in which it issold. Such products include but are not limited to diapers, bibs, wipes;products for and/or methods relating to treating hair (human, dog,and/or cat), including, bleaching, coloring, dyeing, conditioning,shampooing, styling; deodorants and antiperspirants; personal cleansing;cosmetics; skin care including application of creams, lotions, and othertopically applied products for consumer use including fine fragrances;and shaving products, products for and/or methods relating to treatingfabrics, hard surfaces and any other surfaces in the area of fabric andhome care, including: air care including air fresheners and scentdelivery systems, car care, dishwashing, fabric conditioning (includingsoftening and/or freshening), laundry detergency, laundry and rinseadditive and/or care, hard surface cleaning and/or treatment includingfloor and toilet bowl cleaners, and other cleaning for consumer orinstitutional use; products and/or methods relating to bath tissue,facial tissue, paper handkerchiefs, and/or paper towels; tampons,feminine napkins; products and/or methods relating to oral careincluding toothpastes, tooth gels, tooth rinses, denture adhesives, andtooth whitening.

As used herein, the term “surface modifying composition” refers to asubset of consumer products that includes, unless otherwise indicated,beauty care, fabric & home care products. Such products include, but arenot limited to, products for treating hair (human, dog, and/or cat),including, bleaching, coloring, dyeing, conditioning, shampooing,styling; deodorants and antiperspirants; personal cleansing; cosmetics;skin care including application of creams, lotions, and other topicallyapplied products for consumer use including fine fragrances; and shavingproducts, products for treating fabrics, hard surfaces and any othersurfaces in the area of fabric and home care, including: air careincluding air fresheners and scent delivery systems, car care,dishwashing, fabric conditioning (including softening and/orfreshening), laundry detergency, laundry and rinse additive and/or care,hard surface cleaning and/or treatment including floor and toilet bowlcleaners, granular or powder-form all-purpose or “heavy-duty” washingagents, especially cleaning detergents; liquid, gel or paste-formall-purpose washing agents, especially the so-called heavy-duty liquidtypes; liquid fine-fabric detergents; hand dishwashing agents or lightduty dishwashing agents, especially those of the high-foaming type;machine dishwashing agents, including the various tablet, granular,liquid and rinse-aid types for household and institutional use; liquidcleaning and disinfecting agents, including antibacterial hand-washtypes, cleaning bars, mouthwashes, denture cleaners, dentifrice, car orcarpet shampoos, bathroom cleaners including toilet bowl cleaners; hairshampoos and hair-rinses; shower gels, fine fragrances and foam bathsand metal cleaners; as well as cleaning auxiliaries such as bleachadditives and “stain-stick” or pre-treat types, substrate-laden productssuch as dryer added sheets, dry and wetted wipes and pads, nonwovensubstrates, and sponges; as well as sprays and mists all for consumeror/and institutional use; and/or methods relating to oral care includingtoothpastes, tooth gels, tooth rinses, denture adhesives, toothwhitening.

Polysaccharides useful in preparing the modified polysaccharidesaccording to the present invention include a variety of sources fromcellulose to starch to polygalactomannans such as fenugreek gum, guargum, tara gum, locust bean gum and cassia gum. The following structuresare illustrative of various polysaccharides suitable for modificationaccording to the present invention—

Illustrated above is the chemical structure of cellulose, wherein R isH, or hydroxyethylcellulose, wherein at least one R is CH₂CH₂OH.

The above chemical structure is that of starch (amylose molecule). Forthe purpose of the present invention, waxy starches (amylopectinmolecules) are also anticipated to have utility, as well as acombination of both amylose and amylopectin molecules.

Illustrated above is the chemical structure of cassia gum. In additionto molecular weight, cassia gum differs from other gums such as tara gumand guar gum in the ratio of mannose to galactose. From the abovestructure it is seen that cassia gum has a mannose:galactose ratio of5:1. In contrast, the mannose:galactose ratio of locust gum is 4:1, taragum is 3:1, and guar gum is 2:1.

When the polysaccharide is a starch, the source of starch prior tochemical modification can be chosen from a variety of sources such astubers, legumes, cereal, and grains. Non-limiting examples of thisstarch source include corn starch, wheat starch, rice starch, waxy cornstarch, oat starch, cassava starch, waxy barley, waxy rice starch,glutenous rice starch, sweet rice starch, potato starch, tapioca starch,sago starch, or mixtures thereof. Preferred starch sources are lowamylose or waxy starches, including waxy maize, waxy rice, waxy potato,waxy sorghum, waxy cassava and waxy barley.

The above source or base polysaccharides can be in their native form ora modified form. Modified forms or derivatives include physically,enzymatically or chemically modified polysaccharides. Non-limitingexamples of such modifications include thermal modification, acidmodification, oxidation, pyroconversion, crosslinking, acetylation,esterification, hydroxyethylation, hydroxypropylation, phosphorylation,succinate modification, and carboxymethylation among others.

From the above structures it is seen that polysaccharides used as theprecursors for cationic and silicon modification contain hydroxylfunctional groups as part of their structure. These reactive groups areavailable for a wide range of chemical reactions, such as etherificationor esterification. In the case of cationic moieties, quaternary ammoniumgroups can be grafted onto the polymer backbone and become covalentlybound. These cationic groups enhance the polysaccharide's attachment toanionic substrates, such as hair and skin.

Cationic substituents can be introduced into the polysaccharide moleculeby reacting the polysaccharide—preferably in the presence of a catalyst,and typically by an etherification or esterification reaction—with oneor more reagents containing a cationic group, such as a quaternaryammonium, sulfonium or phosphonium group. Preferably the reaction is anetherification reaction and the reagent is a quaternary ammoniumreagent.

When the reagent is a quaternary ammonium reagent, polysaccharidesaccording to the present invention are prepared by reacting thepolysaccharide with a quaternary ammonium salt having a reactivechemical end-group in the presence of a base and in an aqueous orsolvent-based medium. Suitable quaternary ammonium compounds can berepresented by one of the following general formulae (I) and (II)—

wherein

-   -   n is an integer from 1 to 16, preferably 1;    -   X is halogen, particularly fluorine, chlorine, bromine or        iodine, and preferably chlorine;    -   Z=⁻ is an anion which may be inorganic, for example, halide        (fluoride, chloride, bromide or iodide, preferably chloride),        nitrate, nitrite; phosphate, sulfate or hydroxide; or organic,        for example, carboxylate such as acetate or propionate;    -   R is hydrogen or methyl, preferably hydrogen;    -   R¹, R² and R³, which may be the same or different, are each an        organic radical containing up to 10 carbon atoms, preferably        methyl.

Many compounds having the above formulae are known or can be prepared byconventional procedures. Some such compounds are commercially available.Examples of suitable quaternary ammonium compounds include:

-   -   2,3-epoxypropyl-N,N,N-trimethylammonium chloride (a/k/a        glycidyltrimethylammonium chloride (commercially available from        SKW Quab Chemicals Inc. as a 70% aqueous solution under the name        QUAB 151)); and    -   3-chloro-2-hydroxypropyl-N,N,N-trimethylammonium chloride (a/k/a        chlorohydrin (commercially available from Quab Chemicals Inc. as        a 65% aqueous solution under the name of QUAB 188)).        A particularly preferred quaternary ammonium compound is        glycidyltrimethylammonium chloride or its equivalent.

The derivatization reaction with the quaternary ammonium compound can becarried out in a single step or as two or more steps with or withoutintermediate separation and purification of the product. In the singlestep or two or more steps, the reaction is carried out by activating thepolysaccharide with a base, preferably in water or other organicsolvents, followed by reaction with the quaternary ammonium compound.

When the polysaccharide is reacted with the quaternary ammonium compoundin a solvent-based medium, preferably the solvent is one that dispersesor swells the polysaccharide. Suitable solvents include a mixture ofwater with aliphatic alcohols, in particular those having 1-4 carbonatoms; polyalcohols with 2-8 carbon atoms, in particular ethylene anddiethylene glycol and glycerin; aliphatic ketones, in particularacetone; linear and cyclic ethers, in particular dioxane; and aliphaticand aromatic hydrocarbons with 6-15 carbon atoms. For cosmeticapplications, the solvent must be cosmetically or dermatologicallyacceptable, and can comprise water and/or other organic solvents such asC₁-C₄ lower alcohols (e.g., ethanol, isopropanol, tert-butanol orn-butanol); alkylene polyols (e.g., propylene glycol); polyol ethers;and mixtures thereof.

Typically, the quaternary ammonium compound is used in excess, forexample, in a molar ratio based on saccharide units in thepolysaccharide of about 1:16 to about 1:2, more particularly about 1:12to about 1:4. Where the derivatization reaction is carried out in two ormore steps, a molar ratio of about 1:24 to about 1:8 preferably appliesin each step. The base, preferably sodium hydroxide, is used in eachstep in a molar ratio of about 1:140 to about 1:25 based on hydroxylgroups in the monosaccharide units and in a molar ratio of about 2:1 toabout 1:25, preferably about 1:2 to about 1:12, based on the quaternaryammonium compound when this is a compound according to formula (I), orabout 1:2 to about 1:10 when this is a compound according to formula(II). The reaction temperature for each step may be from about 15° C. toabout 120° C., preferably about 50° C. to about 100° C., and thereaction time overall may be, for example, about 1 to about 20 hours.When the derivatization reaction is carried out in two or more stages,the reaction time for each stage is generally about 0.25 to about 5hours, preferably about 0.25 to about 3.5 hours.

The product may be neutralized by treatment with aqueous or organic acid(e.g., hydrochloric acid or lactic acid). The derivatized product can beisolated and purified by removing excess salts and residuals by washing,for example, with water or a mixture of water and solvent. The productis then recovered by filtration and/or centrifugation, and subsequentlydehydrated, for example, by thermal drying. Acetone can optionally beused to remove at least some water and expedite drying.

Derivatized polysaccharides prepared as described above wherein one ormore of R¹, R² and R³ is hydrogen can subsequently be converted by anN-alkylation reaction into the corresponding compounds in which one ormore of R¹, R² and R³ is a hydrocarbon group, for example, with acompound of formula R⁵ Hal where R⁵ is an optionally substitutedhydrocarbon group such as alkyl, hydroxyalkyl or alkenyl, and Hal ishalogen, more particularly fluorine, chlorine, bromine or iodine, toeffect quaternization of some or all of the ammonium groups.

The following structures are illustrative of different types ofcationically modified polysaccharides—

Illustrated above is the chemical structure of starch (amylose molecule)cationically modified with glycidyltrimethylammonium chloride.

The above chemical structure is that of the cassia polymer cationicallymodified with glycidyltrimethylammonium chloride (3.0 mEq/g).

Illustrated above is the chemical structure of the locust bean polymercationically modified with glycidyltrimethylammonium chloride (3.0mEq/g).

Illustrated above is the chemical structure of the tara polymercationically modified with glycidyltrimethylammonium chloride (3.0mEq/g).

Illustrated above is the chemical structure of Polyquaternium-10 (PQ-10)(cationically modified hydroxyethyl cellulose (HEC) (cationicallymodified with glycidyltrimethylammonium chloride)).

Cationically modified polysaccharides according to the present inventiongenerally have a charge density of about 0.1 to about 2.5 meq/g; morepreferably, about 0.2 to about 2.0 meq/g; and even more preferably,about 0.8 to about 1.5 meq/g. As used herein, the “charge density” ofthe cationically modified polysaccharide refers to the ratio of thenumber of positive charges on the polysaccharide to the molecular weightof that polysaccharide.

When the polysaccharide is a gum, the gum has a weight average molecularweight (MW_(w)) of about 50,000 to about 10,000,000 g/mol prior to anydegradation.

Monomeric silicon compounds are known as silanes. Silanes can vary intheir chemistry, as illustrated in the following silane structure—

The above substituents are examples of different types of compounds thatcan bind with silicon. A silane that contains at least onecarbon-silicon bond (e.g., H₃C—Si—) is known as an organosilane. Whenthe other three substituents of the organosilane are all highly reactivehydride, these hydrides can react with water (e.g., by condensationreaction) to yield reactive silanol (—Si—OH) species as illustrated bythe following structure—

Siliconates include organosiliconates such as alkyl siliconates andphenyl siliconates and salts thereof. Salts include sodium and potassiumsalts. Alkali metal alkyl siliconates include those defined by thegeneral formula:

wherein R is an alkyl group containing 1 or more carbons (e.g., methyl,ethyl, propyl, phenyl), and X is an alkali metal (e.g., Na⁺ or K⁺). Forexample, when the alkali metal alkyl siliconate is sodium methylsiliconate, R is methyl and X is sodium. Exemplary species of alkalimetal organosiliconates include sodium methylsiliconate, sodiumethylsiliconate, sodium propylsiliconate, potassium methylsiliconate,potassium ethylsiliconate and potassium propylsiliconate.

Sodium or potassium salts of methyl siliconate are commerciallyavailable as, for example, XIAMETER® OFS-0772 Siliconate (sodium salt)or XIAMETER® OFS-0777 Siliconate (potassium salt) (both available fromDow Corning). For the sodium methyl siliconate product XIAMETER®OFS-0772, the structure above can be illustrated with two hydroxylfunctional groups (—OH) and the third oxygen ionized to OX, where X issodium.

As indicated above, the polysaccharide can optionally be cross-linkedeither in the same reaction as the derivatization reaction or preferablysubsequently thereto. Suitable cross-linking agents for polysaccharidesinclude:

-   -   formaldehyde;    -   methylolated nitrogen compounds such as dimethylolurea        dimethylolethyleneurea and dimethylolimidazolidone;    -   diacarboxylic acids such a maleic acid;    -   dialdehydes such as glyoxal;    -   diepoxides such as 1,2:3,4-diepoxybutane and        1,2:5,6-diepoxyhexane;    -   diisocyanates;    -   divinyl compounds such as divinylsulphone;    -   dihalogen compounds such as dichloroacetone, dichloroacetic        acid, 1,3-dichloropropan-2-ol, dichloroethane,        2,3-dibromo-1-propanol, 2,3-dichloro-1-propanol and        2,2-dichloroethyl ether;    -   halohydrins such as epichlorohydrin;    -   bis(epoxypropyl)ether;    -   vinylcyclohexenedioxide;    -   ethylene glycol-bis(epoxypropyl)ether;    -   1,3-bis(β-hydroxy-Γ-chloropropoxy)-2-propanol;    -   1,3-bis(β-hydroxy-Γ-chloropropoxy)ethane;    -   methylenebis(acrylamide);    -   N,N′-dimethylol(methylenebis(acrylamide));    -   triacrylolhexahydrotriazine;    -   acrylamidomethylene chloroacetamide;    -   phosphates such as phosphorus oxychloride;    -   2,4,6-trichloropyrimidine;    -   2,4,5,6-tetrachloropyrimidine cyanuric chloride;    -   triallylcyanurate phosphorusoxychloride; and    -   bis(acrylamido)acetic acid.

Preferred cross-linking agents include di-epoxy compounds and haloepoxycompounds such as 1,3-bis (glycidyldimethylammonium)propanedichlorideand epichlorohydrin; more preferably phosphate compounds, particularlyphosphorus oxychloride (POCl₃).

When the cross-linking and derivatization reactions are carried outtogether, the conditions are as described above for the derivatizationreaction. When the cross-linking reaction is carried out as a subsequentstep following the derivatization reaction, the reaction conditions arealso generally as described above for the derivatization reaction. Theamount of cross-linking agent required will depend on the nature of theagent, the starting material and the conditions of the cross-linkingreaction. In all cases the reaction should be such as to provide adegree of cross-linking which imparts the desired water insolubility tothe polymer but does not interfere with the water absorption propertiesof the polymer (superabsorbent properties) imparted by the quaternaryammonium group.

Preferably, the cross-linking reaction is carried out at a temperatureof about 15° C. to about 110° C., more preferably about 35° C. to about85° C. for a time of about 1 to about 20 hours, preferably about 2 toabout 10 hours.

The degree of substitution and the degree of cross-linking can both becontrolled by appropriate variation in the amounts of starting materialsand the reaction conditions, in particular, the concentration of thederivatizing and/or cross-linking reagent, reaction time, amount ofbase, reaction temperature, and the nature of the substrate. Dependingupon the type of polysaccharide (e.g., cellulose, starch,polygalactomannan), appropriate modifications will need to be made tothe reaction conditions (e.g., it is known that starch is generally morereactive than cellulose).

The process as described above leads to the polysaccharide derivativewith deprotonated hydroxyl groups as a result of the use of base (e.g.,NaOH) as a catalyst in the derivatization and cross-linking reactions.In general the polysaccharide is required in neutralized form and thiscan be prepared by treatment with acid (e.g., HCl, acetic acid or lacticacid) to neutral pH, or optionally neutralized by washing with water toneutral pH. If necessary, the polysaccharide in its neutral form can bedeprotonated by treatment with strong base (e.g., NaOH), optionallyfollowed by washing with water.

Modified polysaccharides according to the present invention are usefulin a variety of detergent or rinse-off applications, includingindustrial cleaners, household detergents and personal care compositionssuch as shampoos and body washes, as well as leave-on applications suchas car or wood polishes. In general, the formulations include one ormore surfactants, the modified polysaccharide, and a carrier, as well asother ingredients depending upon the formulation's particularapplication.

In one aspect, modified polysaccharides according to the presentinvention are useful in personal care compositions, includingconditioners and conditioning shampoos. Such personal care compositionscomprise, in a cosmetically acceptable medium, a modified polysaccharidehaving both cationic and silicon constituents as described above,preferably in an amount ranging from about 0.1% to about 3.0% by weightrelative to the total weight of the composition (w/w), withconcentrations of from about 0.20% w/w to about 2.0% w/w being morepreferred, even more preferably from about 0.25% w/w to about 1.5% w/w.

The term “cosmetically acceptable medium” refers to a medium that iscompatible with at least one keratin material (e.g., skin, hair, nails,eyelashes, eyebrows, lips and any other area of body or facial skin).Such cosmetically acceptable medium can consists solely of water, or amixture of water and a cosmetically acceptable solvent such as a C₁-C₄lower alcohol (e.g., ethanol, isopropanol, tert-butanol or n-butanol);alkylene polyols (e.g., propylene glycol); polyol ethers; and mixturesthereof.

Personal care compositions according to the invention include those ofthe “rinse-off” category. These include, for example, shampoos,rinse-off conditioners, body washes, facial washes, liquid and barsoaps, hydro-alcoholic based products such as hand sanitizers and soforth which can be readily washed off with water. Personal carecompositions according to the invention include those of the “leave-on”category, such as sunscreens, lotions, combing creams, insect repellantsand so forth which are intended to remain on the skin or hair for anextended period. Additional leave-ons include color cosmetics such aspigmented skin colorants, nail polish and nail polish remover, mascara,rouge, lipstick and balm.

The composition according to the invention can also comprise one or morestandard additives well known in the art, such as anionic, cationic,nonionic, amphoteric or zwitterionic surfactants; anionic, cationic,nonionic, amphoteric or zwitterionic polymers; thickeners; nacreousagents; opacifiers; UV-screening agents; fragrances; mineral, plantand/or synthetic oils; fatty acid esters; dyes; mineral or organic,natural or synthetic particles; preserving agents; and pH stabilizers.Surfactants can be present in the composition in an amount from about 5wt % to about 60 wt % by weight of the composition. Other optionaladditives are generally present in the composition according to theinvention in an amount ranging from about 0 to about 20% by weight,based on total weight of the composition. One skilled in the art willselect these optional additives and their amount in a manner such thatthey do not harm the properties of the compositions of the presentinvention.

Anionic surfactants useful in the surface modifying compositions includeammonium lauryl sulfate, ammonium laureth sulfate, triethylamine laurylsulfate, monoethanolamine lauryl sulfate, monoethanolamine laurethsulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate,triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocyl sulfate,ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate,potassium cocoyl sulfate, potassium lauroyl sulfate, monoethanolaminecocoyl sulfate, and combinations thereof.

Other suitable anionic surfactants include the reaction product of fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide where the fatty acids are derived from, for example, coconutoil or palm kernel oil, and sodium or potassium salts of fatty acidamides of methyl tauride.

Still other anionic surfactants suitable for use in the surfacemodifying compositions include various succinnates, examples of whichinclude disodium N-octadecylsulfosuccinnate, disodium laurylsulfosuccinate, diammonium lauryl sulfosuccinate, tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate, diamyl esters ofsodium sulfosuccinic acid, dihexyl esters of sodium sulfosuccinic acid,and dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic surfactants also include olefin sulfonates havingabout 10 to about 24 carbon atoms. Olefin sulfonates refer to thosecompounds that can be produce by sulfonation of α-olefins usinguncomplexed sulfur trioxide, followed by neutralization of the acidreaction mixture under conditions such that any sulfones formed in thereaction are hydrolyzed to give the correspondinghydroxy-alkanesulfonates. The α-olefins from which the olefin sulfonatesare derived are preferably mono-olefins having from about 10 to about 24carbon atoms, preferably from about 12 to about 16 carbon atoms.Preferably, they are straight chain olefins.

Another class of anionic surfactants suitable for use herein aref-alkyloxy alkane sulfonates. Such surfactants conform to the followingformula—

where R¹ is a straight chain alkyl group having from about 6 to about 20carbon atoms; R² is a lower alkyl group having from about 1 to about 3carbon atoms, preferably 1 carbon atom; and M is a water-soluble cation.

In addition to the sulfates, isethinoates, sulfonates andsulfosuccinates described above, other potential anions for the anionicsurfactant include phosphonates, phosphates and carboxylates.

Surface modifying compositions according to the present invention canalso include one or more additional surfactants such as amphotericsurfactants, zwitteronic surfactants, cationic surfactants and nonionicsurfactants. Suitable amphoteric, zwitteronic, cationic and nonionicsurfactants for use herein include those known for use in hair care orother personal care compositions (e.g., cocamidopropyl betaine and/orlauramidopropyl betaine). The concentration of such surfactantspreferably ranges from about 0.5% to about 20.0% w/w, preferably fromabout 1.0% to about 10.0% by weight of the composition.

The surfactants are preferably present in the surface modifyingcompositions at concentrations of about 35% or less, more preferablyabout 20% or less, and even more preferably about 15% or less by weightof the composition.

Other optional ingredients include compounds and ingredients that modifythe aesthetics of the final composition. For example, fragrances andnatural oils can be used to provide a desirable odor, while dyes,pigments, opacifying or pearlescent agents can be used to impart a moreappealing appearance. From a performance perspective, vitamins, aminoacids and humectants can provide enhanced protective and reparativefunctionality. Of particular use are ingredients that protect, prolongor enhance the intensity of hair colorants or skin and nail coloringcompositions.

Non-detersive conditioning agents useful in the practice of theinvention can be selected from a variety of categories. Particularlyuseful conditioning agents include oily substances, waxes, nonionicsubstances, cationic ingredients, amphiphilic ingredients, cationicpolymers and mixtures thereof. Oily substances include natural oils(e.g., olive oil, almond oil, wheat germ oil, ricinus oil) and syntheticoils (e.g., mineral oil, isopropyl myristate, palmitate, stearate andisostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyladipate, dioctyl adipate, myristyl myristate and oleyl erucate.

Moisturizing agents such as panthenols and polyols (e.g., glycerol,polyethylene glycols having a molecular weight from about 200 to about20,000) can also be present as non-detersive conditioning agents. Themoisturizing ingredients can be present in the compositions at aconcentration of about 0.01 to about 2.5% by weight of the totalcomposition. Additional moisturizing agents include ester-basedemollients such as cetyl lactate, lauryl lactate, C₁₂ to C₁₅ lactate,dicetyl malate, myristyl lactate, decyl oleate, isodecyl oleate,diisopropyl adipate, isocetyl alcohol, isodecyl neopentanoate,ethylhexyl palmitate, isocetyl stearate, myristyl myristate and myristyllaurate, glycidyl dilaurate, tridecyl neopentanoate, isostearylneopentanoate, octyldodecyl stearate, isocetyl stearoyl stearate,octyldodecyl stearoyl stearate, and carpylic/capric triglyceride.

Nonionic conditioning agents can be present in the composition in arange of from about 0.01% to about 10.00% by weight of the totalcomposition, preferably about 0.05% to about 7.50%, more preferablyabout 0.10% to about 5.00%, and most preferably about 0.10% to about3.00% by weight of the total composition.

Other cationic ingredients can also be used as non-detersiveconditioning agents such as cetyltrimethyl ammonium chloride,steartrimonium chloride, behentrimonium chloride, stearamidopropyltrimonuim chloride, dioleoylethyl dimethyl ammonium methosulfate, anddioleoylethyl hydroxyethylmonium methosulfate. Amido amines such asstearamidopropyl dimethyl amine can also be used as a conditioningcationic surfactant in compositions of the present invention.

Other suitable conditioning ingredients include glyceryl ethers such asglyceryl butyl ether, glyceryl isobutyl ether, glyceryl tert-butylether, glyceryl pentyl ether, glyceryl isopentyl ether, glyceryl hexylether, glyceryl isohexyl ether, glyceryl heptyl ether, glyceryl octylether, glyceryl ethylhexyl ether, glyceryl nonyl ether, glyceryl decylether, glyceryl isodecyl ether, glyceryl lauryl ether, glyceryl myristylether, glyceryl palmityl ether, glyceryl stearyl ether and glycerylbehenyl ether and their mixtures. Most preferred are glyceryl butylether, glyceryl isobutyl ether, glyceryl tert-butyl ether, glycerylpentyl ether, glyceryl isopentyl ether, glyceryl hexyl ether, glycerylisohexyl ether, glyceryl heptyl ether, glyceryl octyl ether, glycerylethylhexyl ether, glyceryl nonyl ether, glyceryl decyl ether, glycerylisodecyl ether are glyceryl lauryl ether, and the like.

Still other non-detersive conditioning ingredients include polyphenolssuch as those derived from aqueous and alcoholic plant extracts.Suitable extracts include those derived from aloe, pineapple, artichoke,arnica, avocado, valerian, bamboo, henbane, birch, stinging nettle,echinacea, ivy, wild angelica, gentian, ferns, pine needles, silverweed, ginseng, broom, oat, rose hip, hamamelis, hay flowers, elderberry,hop, coltsfoot, currants, chamomile, carrots, chestnuts, clover, burrroot, coconut, cornflower, lime blossom, lily of the valley, marinealgae, balm, mistletoe, passion flower, ratanhia, marigold, rosemary,horse chestnut, pink hawthorn, sage, horsetail, yarrow, primrose,nettle, thyme, walnut, wine leaves, white hawthorn and the like.

Personal care formulations according to the present invention can alsocontain other ingredients for improving their appearance and consumerappeal such as fragrances, dyes, colorants, pigments, bleaches,pearlescent agents (e.g., mica and titanium dioxide coated mica),opacifying agents and the like. Rheology modifiers such as carbomer,poly(vinylpyrrolidone), hydroxypropyl methylcellulose, hydroxypropylcellulose, sodium polyacrylates can be employed to provide thickening orother aesthetically-pleasing characteristics.

For a more detailed understanding of the invention, reference can bemade to the following examples, which are intended as furtherillustrations of the invention but are not to be construed in a limitingsense. All parts and percentages are by weight unless stated otherwise.

EXAMPLES Example 1—Modified Polysaccharide Preparation

Various samples of modified tara gum were prepared having differentamounts of cationization as well as different amounts of siliconconstituents for comparison. An additional comparative sample wasprepared having only cationic modification.

The method of preparing the modified polysaccharide samples was asfollows. An aqueous solution of isopropanol, NaOH and tara gum was mixedtogether with stirring at 60° C. Glycidyltrimethylammonium chloride wasadded to the solution and allowed to react with the tara gum for 3 hoursat 60° C. The cationically modified mixture was then cooled to 40° C.After cooling to 40° C., the cationically modified gums were reactedwith sodium methylsiliconate (with the exception of comparative Example5, to which no silicone modification was performed) in the amountindicated in the above Table for 1 hour, followed by neutralization ofthe modified gums with HCl, then filtration, and subsequent washing with80% isopropanol. The samples were then dried overnight at 40° C. Theformulae used in forming the modified polysaccharides are provided inthe following Table:

TABLE 1 Modified Polysaccharide Formulae Sample ID 5 Ingredient (wt %)¹1 2 3 4 (comparative) Tara gum 100% 100% 100% 100% 100% Isopropanol(90%) 167% 167% 167% 167% 167% NaOH (25%)² 12% 12% 12% 12% 12%glycidyltrimethylammonium 18% 18% 18% 28% 18% chloride³ sodiummethylsiliconate⁴ 6% 12% 24% 24% 0% HCl (3M)⁵ 28-47% 28-47% 28-47%28-47% 28-47% Isopropanol (80%) 400% 400% 400% 400% 400% ¹Wt % isrelative to 100% polysaccharide used. ²12% based on aqueous 25% NaOHweight (anhydrous NaOH weight would be 3%). ³QUAB ® 151(glycidyltrimethylammonium chloride), commercially available from SKWQuab Chemicals Inc., Saddle Brook, New Jersey USA. ⁴XIAMETER ® OFS-0772Siliconate (sodium methyl siliconate), commercially available from DowChemical, Midland, Michigan USA. ⁵Targeted pH for the neutralizationstep is in the range of 4 to 7. Hence, the amount of 3M HCl required toneutralize this product is presented as a range.

Dried modified tam gum was analyzed in radial mode using a ThermoScientific™ iCAP™ 7000 Series ICP-OES (Inductively CoupledPlasma-Optical Emission Spectroscopy) at silicon wavelength 221.667 nmin order to determine the amount of silicon bonded to the gum. Theresults are provided in Table 2 below—

TABLE 2 Silicon Bound to Polysaccharide Sample Silicon¹ Cationic² IDTreatment (%) Treatment (%) Si (ppm) 1 6 18 782 ± 5.56 2 12 18 1919 ±26.12 3 24 18 2915 ± 71.16 4 24 28 1782 ± 43.16 5 0 18 Below DetectionLimit ¹XIAMETER ® OFS-0772 Siliconate (sodium methyl siliconate),commercially available from Dow Chemical, Midland, Michigan USA. ²QUAB ®151 (glycidyltrimethylammonium chloride), commercially available fromSKW Quab Chemicals, Inc., Saddle Brook, New Jersey USA.

The above results illustrate firstly incorporation of silicon into acationic tara gum backbone. As the amount of silicon (XIAMETER®OFS-0772) level increases (from 6 to 24%, Samples 1 through 3) theamount of bound silicon increases. Secondly, it is seen that anincreased degree of tara gum quaternization results in a lower degree ofsiliconation (sample 4). This phenomenon can be possibly explained bythe reduced amount of available binding sites for the silicon (XIAMETER®OFS-0772) and/or increased steric hindrance that inhibits silicon accessto the cationic tara gum backbone. Therefore, careful adjustment of bothsubstituents is required to obtain maximum performance in bothdeposition (via quaternization) and sensory benefits (via siliconation).

Example 2—Shampoo Formulation

Conditioning properties of a standard shampoo composition containingvarious modified polysaccharides were evaluated. All testing wasperformed on hair procured from International Hair Importers & Products(Glendale, N.Y.). Hair tresses weighed approximately 3 g and measured 8inches (20.32 cm) in length and 1 inch (2.54 cm) in width. Prior totesting, the tresses were bleached using a 6% hydrogen peroxide at a pHof 10.2. The tresses were left in contact with the bleach solution for40 minutes under controlled temperature conditions (40° C.). At the endof this process, tresses were thoroughly rinsed under an Intellifaucetrinsing apparatus set at 40° C. with a controlled flow rate of 1.0 GPM.Various shampoo formulations with and without modified polysaccharideswere produced and tested according to the following formulations—

TABLE 3 Shampoo Formulations Basic Shampoo Control 1¹ Control 2² Shampoo1 Shampoo Ingredients (wt %) (wt %) (wt %) 2 (wt %) Deionized water53.95 52.31 54.15 54.15 Sample 1³ — — 0.25 — Sample 2 — — — 0.25Polyquaternium-10⁴ 0.25 0.25 — — Polydimethylsiloxane⁵ — 1.64 — —Surfactant blend⁶ 44.00 44.00 44.00 44.00 Lactic Acid⁷ 1.30 1.30 1.101.10 Preservative⁸ 0.50 0.50 0.50 0.50 Total 100.00 100.00 100.00 100.00¹Control 1 is a shampoo formulation having only cationic charge(Polyquaternium-10) and no modified polysaccharide according to theinvention. ²Control 2 (comparative) is a shampoo formulation having bothcationic charge (Polyquaternium-10) and addition of silicon as aseparate ingredient but no modified polysaccharide according to theinvention. ³See Table 1 above for Sample 1 and Sample 2 ⁴UCARE ™ PolymerJR-30M, available from The Dow Chemical Company, Midland Michigan USA.⁵XIAMETER ® MEM-1785 Emulsion (INCI: Dimethiconol (and) TEA-Dodecylbenzenesulfonate), available from Dow Corning, Midland, MichiganUSA. ⁶Miracare ® Plaisant (INCI: Aqua (and) Sodium Cocoyl Isethionate(and) Sodium Lauroamphoacetate (and) Sodium Methyl Cocoyl Taurate),available from Solvay Novecare, Princeton, New Jersey USA. ⁷PURAC ®HiPure 90, available from Corbion, Amsterdam, The Netherlands.⁸Microcare ® PHI (INCI: Phenoxyethanol (and) IodopropynylButylcarbamate), available from Thor Personal Care SAS, La CroixSaint-Ouen, France.

All product treatments were conducted according to the followingprocedure. Shampoo was applied at a quantity of 0.1 g/g of hair ofshampoo applied to tress of wet hair and massaged in between thumb andforefinger for thirty (30) seconds. The tress was then rinsed underIntellifaucet rinsing apparatus set at 38° C. and 1 gal/min for 30seconds.

Shampoo Results—

The primary technical function of most conditioning products is tolubricate the hair surface and, in doing so, facilitate manageabilityand provide detangling benefits and lower combing friction. Comparativeresults of shampoo formulations containing modified polysaccharidesaccording to the invention against control formulations are shown in thefollowing Tables. Results are based on testing using five (5) panelistsand presented as the average of the score cards from 1 to 5, with 5being the best. Positive results for the modified polysaccharideformulations should show those formulations to be comparative to orbetter than formulations containing PQ-10 and silicon separately(Control 2 Shampoo above).

TABLE 4 Wet Feel Results (Panelists Averaged Score card) (Shampoos wereformulated according to the recipe described in Table 3) Control 2Control 3¹ Control 4⁴ Shampoo 1 Shampoo 1 5 3 4 1 5 4 4 2 4 3 3 2 4 2 31 5 3 4 Total Score: 7 Total Score: 23 Total Score: 15 Total Score: 18¹Control 3 represents a negative control (a 15% SLES only (surfactantonly)) solution; i.e., the hair tresses were washed using only asurfactant solution and evaluated. ²Control 4 represent commercialshampoo (Dove Daily Moisture Shampoo & Conditioner) comparative; i.e.,the hair tresses were washed using the commercial shampoo and evaluated.

TABLE 5 Wet Comb Results (Panelists Averaged Score card) (Shampoos wereformulated according to the recipe described in Table 3) Control 3Control 4 Shampoo 1 Control 2 1 5 3 4 1 5 3 4 1 5 4 3 1 5 2 4 1 5 4 4Total Score: 5 Total Score: 25 Total Score: 16 Total Score: 19

TABLE 6 Dry Feel Results (Panelists Averaged Score card) (Shampoos wereformulated according to the recipe described in Table 3) Control 3Control 4 Shampoo 1 Control 2 3 5 5 4 3 5 5 5 4 5 5 4 3 5 5 4 4 5 4 4Total Score: 17 Total Score: 25 Total Score: 24 Total Score: 21

TABLE 7 Results from Dry Comb (Panelists Averaged Score card) (Shampooswere formulated according to the recipe described in Table 3) Control 3Control 4 Shampoo 1 Control 2 3 5 4 4 3 5 3 4 4 5 4 5 3 5 5 4 3 5 4 5Total Total Total Total Score: 16 Score: 25 Score: 20 Score: 22

The results show that the formulations of the invention (Sample 1modified polysaccharide with 18% cationization and 6% silicon—Shampoo 1)are equivalent to or better than the Control 2 Shampoo having both PQ10and silicon as separate ingredients.

As will be appreciated by one skilled in the art, the invention providesa wide variety of industrial, home care and personal care surfacemodifying formulations. For example, the invention provides a widevariety of cosmetic and dermatologically acceptable personal careformulations as exemplified below. Those of ordinary skill in the artwill appreciate that these formulations can be modified, and that otherpersonal care formulations can be produced using the modifiedpolysaccharides described herein.

Example of formulations in which the modified polysaccharide can be usedare as follows—

TABLE 8 Shampoo with no Silicone Ingredient Wt % Deionized water 74.88Modified polysaccharide ¹ 0.50 Sodium Laureth Sulfate ² 12.85Cocamidopropyl Betaine ³ 8.57 Sodium Chloride 1.00 Fragrance (Parfum)0.60 Disodium EDTA ⁴ 0.10 Lactic acid ⁵ 1.00 Preservative ⁶ 0.50 Total100.00 ¹ Modified polysaccharide according to the invention (e.g.,Sample 1 or Sample 2 above). ² TEXAPON ® N 70 NA anionic surfactant,available from BASF Corporation, Florham Park, New Jersey USA. ³AMPHOSOL ® CG amphoteric surfactant, available from Stepan Company,Northfield, Illinois USA. ⁴ Edeta ® BD amino-carboxylic acid, availablefrom BASF Corporation, Florham Park, New Jersey USA. ⁵ PURAC ® HiPure90, available from Corbion, Amsterdam, The Netherlands. ⁶ Microcare ®PHI (INCI: Phenoxyethanol (and) Iodopropynyl Butylcarbamate), availablefrom Thor Personal Care SAS, LaCroix Saint-Ouen, France.

TABLE 9 Rinse-Off Conditioner Ingredient Wt % Deionized water 87.25Modified polysaccharide ¹ 0.50 Disodium EDTA ² 0.10 Emulsifier ³ 2.00Alcohol ⁴ 2.00 Alcohol ⁵ 4.00 Silicone ⁶ 0.50 Silicone ⁷ 2.00 Fragrance(Parfum) 0.5 Lactic acid ⁸ 0.65 Preservative ⁹ 0.50 Total 100.00 ¹Modified polysaccharide according to the invention (e.g., Sample 1 orSample 2 above). ² Edeta ® BD amino-carboxylic acid, available from BASFCorporation, Florham Park, New Jersey USA. ³ Lexamine ® S-13 waxemulsifier (INCI: Stearamidopropyl Dimethylamine), available fromInolex, Philadelphia, Pennsylvania USA. ⁴ Lanette ® 16 viscosifier(INCI: Cetyl Alcohol), available from BASF Corporation, Florham Park,New Jersey USA. ⁵ Lanette ® 18 viscosifier (INCI: Stearyl Alcohol),available from BASF Corporation, Florham Park, New Jersey USA. ⁶XIAMETER ® PMX-200 silicone fluid (INCI: Dimethicone), available fromDow Corning, Midland, Michigan USA. ⁷ XIAMETER ® PMX-0345 cyclosiloxaneblend (INCI: Cyclopentasiloxane (and) Cyclohexasiloxane), available fromDow Corning, Midland, Michigan USA. ⁸ PURAC ® HiPure 90, available fromCorbion, Amsterdam, The Netherlands. ⁹ Microcare ® SBB, liquid blend ofbenzyl alcohol, benzoic acid and sorbic acid, available from ThorPersonal Care SAS, La Croix Saint-Ouen, France.

TABLE 10 Leave-In Moisturizer Ingredient Wt % Deionized water 95.60Modified polysaccharide ¹ 0.35 Silicon fluid ² 1.00 Silicon emulsion ³1.50 Fragrance (Parfum) 0.40 Nonionic surfactant ⁴ 0.40 Lactic acid ⁵0.25 Preservative ⁶ 0.50 Total 100.00 ¹ Modified polysaccharideaccording to the invention (e.g., Sample 1 or Sample 2 above). ²XIAMETER ® OFX-0193 silicone fluid (INCI: PEG-12 Dimethicone), availablefrom Dow Corning, Midland, Michigan USA. ³ XIAMETER ® MEM-0949 cationicsilicon polymer emulsion (INCI: Amodimethicone (and) CetrimoniumChloride (and) Trideceth-12), available from Dow Corning, Midland,Michigan USA. ⁴ Brij ® O20 (INCI: Oleth-20), available from CrodaInternational Plc, East Yorkshire, England. ⁵ PURAC ® HiPure 90,available from Corbion, Amsterdam, The Netherlands. ⁶ Microcare ® SBB,liquid blend of benzyl alcohol, benzoic acid and sorbic acid, availablefrom Thor Personal Care SAS, La Croix Saint-Ouen, France.

TABLE 11 Hair Oil Moisturizer Ingredient % Deionized water 87.90Modified polysaccharide ¹ 0.50 Propylene glycol 2.00 Coconut oil ² 4.00Sunflower oil ³ 4.00 Fragrance (Parfum) 0.60 Lactic acid ⁴ 0.50Preservative ⁵ 0.50 Salcare SC 96 ⁶ 2.50 Total 100.00 ¹ Modifiedpolysaccharide according to the invention (e.g., Sample 1 or Sample 2above). ² Rita Coconut Oil 76 (INCI: Cocos Nucifera (Coconut) Oil),available from RITA Corporation, Crystal Lake, Illinois USA. ³Florasun ® 90 sunflower oil (INCI: Helianthus Annus (Sunflower) SeedOil), available from FloraTech, Chandler, Arizona USA. ⁴ PURAC ® HiPure90, available from Corbion, Amsterdam, The Netherlands. ⁵ Microcare ®SBB, liquid blend of benzyl alcohol, benzoic acid and sorbic acid,available from Thor Personal Care SAS, La Croix Saint-Ouen, France. ⁶Salcare ® SC 96 cationic homopolymer moisturizer (INCI:Polyquaternium-37, Propylene Glycol Dicaprylate/Dicaprate, PPG-1Trideceth-6), available from BASF Corporation, Florham Park, New JerseyUSA.

TABLE 12 Sulfate-Free Shampoo Ingredient Wt % Wt % Wt % Wt % Deionizedwater 69.95 86.90 69.95 86.90 Sample 1 ¹ 0.80 0.80 Sample 2 ¹ 0.80 0.80Amphoteric surfactant ² 16.67 10.00 16.67 10.00 Anionic surfactant ³11.28 1.00 11.28 1.00 Chelating agent ⁴ 0.10 0.10 0.10 0.10 Fragrance(Parfum) 0.60 0.60 0.60 0.60 Lactic Acid ⁵ 0.10 0.10 0.10 0.10Preservative ⁶ 0.50 0.50 0.50 0.50 Total 100.00 100.00 100.00 100.00 ¹See Table 1 above. ² AMPHOSOL ® CBD SPECIAL (INCI: Cetyl Betaine),available from the Stepan Company, Northfield, Illinois USA. ³Hostapon ® SCI-85 C (INCI: Sodium Cocoyl Isethionate), available fromClariant International Ltd., Muttenz, Switzerland. ⁴ EDETA ® BX Powder(INCI: Tetrasodium EDTA), available from BASF, Ludwigshafen, Germany. ⁵PURAC ® HiPure 90, available from Corbion, Amsterdam, The Netherlands. ⁶Microcare ® SBB, liquid blend of benzyl alcohol, benzoic acid and sorbicacid, available from Thor Personal Care SAS, La Croix Saint-Ouen,France.

TABLE 13 Sulfate-Free Body Wash Ingredient Wt % DI Water 65.95 ModifiedPolysaccharide ¹ 0.80 Humectant ² 2.00 Amphoteric surfactant ³ 16.67Anionic surfactant ⁴ 11.28 Opacifier ⁵ 1.50 Chelating agent ⁶ 0.10Fragrance (Parfum) 0.60 Lactic acid ⁷ 0.10 Preservative ⁸ 1.00 Total100.00 ¹ Modified polysaccharide according to the invention (e.g.,Sample 1 or Sample 2 above). ² Glystar ® A-31 (INCI: Hydrogenated StarchHydrolysate), available from Ingredion Inc., Westchester, Illinois USA.³ AMPHOSOL ® CBD SPECIAL (INCI: Cetyl Betaine), available from theStepan Company, Northfield, Illinois USA. ⁴ Hostapon ® SCI-85 C (INCI:Sodium Cocoyl Isethionate), available from Clariant International Ltd.,Muttenz, Switzerland. ⁵ Cutina ® EGMS (INCI: Glycol Stearate), availablefrom BASF Corporation, Florham Park, New Jersey USA. ⁶ EDETA ® BX Powder(INCI: Tetrasodium EDTA), available from BASF, Ludwigshafen, Germany. ⁷PURAC ® HiPure 90, available from Corbion, Amsterdam, The Netherlands. ⁸Microcare ® SBB, liquid blend of benzyl alcohol, benzoic acid and sorbicacid, available from Thor Personal Care SAS, La Croix Saint-Ouen,France.

TABLE 14 Body Wash Ingredient Wt % DI Water 42.99 ModifiedPolysaccharide ¹ 0.60 Humectant ² 2.00 Amphoteric surfactant ³ 14.29Anionic surfactant ⁴ 36.67 Opacifier ⁵ 1.50 Chelating agent ⁶ 0.25Fragrance (Parfum) 0.60 Lactic acid ⁷ 0.10 Ammonium Chloride 0.50Preservative ⁸ 0.50 Total 100.00 ¹ Modified polysaccharide according tothe invention (e.g., Sample 1 or Sample 2 above). 2 Glystar ® A-31(INCI: Hydrogenated Starch Hydrolysate), available from Ingredion Inc.,Westchester, Illinois USA. ³ AMPHOSOL ® HCG-HP (INCI: CocamidopropylBetaine), available from the Stepan Company, Northfield, Illinois USA. ⁴Calfoam ® ES-302 (INCI: Sodium Lauryl Ether Sulfate), available fromClariant International Ltd., Muttenz, Switzerland. ⁵ Cutina ® EGMS(INCI: Glycol Stearate), available from BASF Corporation, Florham Park,New Jersey USA. ⁶ EDETA ® BX Powder (INCI: Tetrasodium EDTA), availablefrom BASF, Ludwigshafen, Germany. ⁷ PURAC ® HiPure 90, available fromCorbion, Amsterdam, The Netherlands. ⁸ Microcare ® SBB, liquid blend ofbenzyl alcohol, benzoic acid and sorbic acid, available from ThorPersonal Care SAS, La Croix Saint-Ouen, France.

TABLE 15 Styling Lotion Ingredient Wt % DI Water 93.00 ModifiedPolysaccharide ¹ 0.75 Cationic Copolymer ² 3.00 Moisturizer ³ 0.50Lactic acid ⁴ 0.25 Preservative ⁵ 1.00 Fragrance (Parfum) 0.50 Nonionicsurfactant ⁶ 1.00 Total 100.00 ¹ Modified polysaccharide according tothe invention (e.g., Sample 1 or Sample 2 above). ² Gafquat ® 755N(INCI: Polyquaternium-11), available from Ashland Inc., Covington,Kentucky USA. ³ Solulan ® 75 Lanolin Derivative (INCI: PEG-75 Lanolin),available from Lubrizol Advanced Materials, Cleveland, Ohio USA. ⁴PURAC ® HiPure 90, available from Corbion, Amsterdam, The Netherlands. ⁵Microcare ® SBB, liquid blend of benzyl alcohol, benzoic acid and sorbicacid, available from Thor Personal Care SAS, La Croix Saint-Ouen,France. ⁶ Brij ® O20 (INCI: Oleth-20) (Chemical Descriptor:Polyoxyethylene (20) oleyl ether), available from Croda InternationalPLC, Snaith, Goole, East Yorkshire, United Kingdom.

TABLE 16 Combing Cream Ingredient Wt % DI Water 85.75 ModifiedPolysaccharide ¹ 0.50 Propylene Glycol 2.00 Fixative polymer ² 2.00Cetearyl Alcohol 2.50 Cationic Surfactant ³ 2.00 Silicone fluid ⁴ 2.00Lactic acid ⁵ 0.25 Preservative ⁶ 1.00 Fragrance (Parfum) 0.50Moisturizer ⁷ 1.50 Total 100.00 ¹ Modified polysaccharide according tothe invention (e.g., Sample 1 or Sample 2 above). ² Styleze ® W-10(INCI: Polyquaternium-55) (Chemical Descriptor:Vinylpyrrolidone/Dimethylaminopropylmethacrylamide/Methacryloylaminopropyl Lauryl Dimethyl AmmoniumChloride Terpolymer), available from Ashland Inc., Covington, KentuckyUSA. ³ Genamin ® KDMP (INCI: Behentrimonium Chloride), available fromClariant, Muttenz, Switzerland. ⁴ XIAMETER ® PMX-200 silicone fluid(INCI: Dimethicone), available from Dow Corning, Midland, Michigan USA.⁵ PURAC ® HiPure 90, available from Corbion, Amsterdam, The Netherlands.⁶ Microcare ® SBB, liquid blend of benzyl alcohol, benzoic acid andsorbic acid, available from Thor Personal Care SAS, La Croix Saint-Ouen,France. ⁷ Salcare ® SC 96 cationic homopolymer moisturizer (INCI:Polyquaternium-37, Propylene Glycol Dicaprylate/Dicaprate, PPG-1Trideceth-6), available from BASF Corporation, Florham Park, New JerseyUSA.

TABLE 17 Moisturizing Lotion Ingredient Wt % DI Water 79.51 Modifiedpolysaccharide ¹ 0.50 Glycerin 2.00 Antimicrobial ² 0.10 Emollient ³3.00 Nonionic surfactant ⁴ 4.00 Nonionic surfactant ⁵ 4.00 Shea butter ⁶1.00 Sunflower Oil ⁷ 2.00 Cocoa Butter ⁸ 0.50 25% Sodium Hydroxide 0.060Lactic acid ⁹ 0.030 Chelating agent ¹⁰ 0.10 Allantoin ¹¹ 0.25 Humectant¹² 1.00 Silicon fluid ¹³ 1.00 Fragrance (Parfum) 0.75 Nipaguard DMDMH ¹⁴0.2 Total 100.00 ¹ Modified polysaccharide according to the invention(e.g., Sample 1 or Sample 2 above). ² Nipagin ® M Sodium (INCI: SodiumMethylparaben), available from Clariant, Muttenz, Switzerland. ³Ritamollient CCT (INCI: Caprylic/Capric Triglyceride), available fromRita Corporation, Crystal Lake, Illinois USA. ⁴ Promulgen ™ D NonionicEmulsifier (INCI: Cetearyl Alcohol (and) Ceteareth-20), available fromLubrizol Advanced Materials, Cleveland, Ohio USA. ⁵ Promulgen ™ GNonionic Emulsifier (INCI: Stearyl Alcohol (and) Ceteareth-20),available from Lubrizol Advanced Materials, Cleveland, Ohio USA. ⁶ ShebuRefined (INCI: Butyrospermum Parkii (Shea Butter)), available from RitaCorporation, Crystal Lake, Illinois USA. ⁷ Rita SSO (INCI: HelianthusAnnuus (Sunflower) Seed Oil), available from Rita Corporation, CrystalLake, Illinois USA. ⁸ Rita Cocoa Butter NF (INCI: Theobroma Cacao(Cocoa) Seed Butter), available from Rita Corporation, Crystal Lake,Illinois USA. ⁹ PURAC ® HiPure 90, available from Corbion, Amsterdam,The Netherlands. ¹⁰ EDETA ® BD (INCI: Disodium EDTA), available fromBASF, Ludwigshafen, Germany. ¹¹ RonaCare ® Allantoin (INCI: Allantoin),available from Merck KGaA, Darmstadt, Germany. ¹² AJIDEW ® NL-50 (INCI:Sodium PCA (and) Aqua), available from Ajinomoto Co., Inc., Tokyo,Japan. ¹³ XIAMETER ® PMX-200 silicone fluid (350 cps) (INCI:Dimethicone), available from Dow Corning, Midland, Michigan USA. ¹⁴Nipaguard ® DMDMH (INCI: DMDM Hydantoin), available from ClariantMuttenz, Switzerland.

TABLE 18 Hand Sanitizer Ingredient Wt % DI Water 32.05 ModifiedPolysaccharide ¹ 0.40 Denatured alcohol 62.00 Glycerin 5.00 Chelatingagent ² 0.05 Fragrance (Parfum) 0.50 Total 100.00 ¹ Modifiedpolysaccharide according to the invention (e.g., Sample 1 or Sample 2above). ² EDETA ® BX Powder (INCI: Tetrasodium EDTA), available fromBASF, Ludwigshafen, Germany.

The invention further provides a wide variety of industrial and homecare formulations as exemplified below. Those of ordinary skill in theart will appreciate that these formulations can be modified, and thatother formulations can be produced using the modified polysaccharidesdescribed herein.

Examples of industrial and home care formulations in which the modifiedpolysaccharide can be used are as follows—

TABLE 19 Protective Coating for Automotive Painted Surface Ingredient Wt% Wt % Modified Polysaccharide ¹ 30-50 30-50 Aminofunctional siloxane ²15-20 — Alkylarylpolysiloxane fluid ³ — 15-30 Propylene glycol 3-5Detergent ⁴ 52-25 52-25 ¹ Modified polysaccharide according to theinvention (e.g., Sample 1 or Sample 2 above). ² XIAMETER ® OFX-0536Fluid (amino methoxy functional polydimethylsiloxane), available fromavailable from Dow Corning, Midland, Michigan USA. ³ XIAMETER ® OFX-0203Fluid (100% active alkylaryl polysiloxane fluid), available fromavailable from Dow Corning, Midland, Michigan USA. ⁴ Dawn ® dishwashingliquid, available from The Procter & Gamble Company, Cincinnati, OhioUSA.

TABLE 20 Fabric Treatment Compositions INGREDIENTS (Wt %) Formula 1Formula 2 Formula 3 Formula 4 Modified polysaccharide ¹ 6.81% 7.48%9.00% 11.9% Nonionic surfactant ² 0.60% 0.60% 0.60% 0.22% Monopropyleneglycol ³ 0.00% 3.45% 3.88% 1.81% Glycerol 5.00% 5.00% 5.00% 0.77%Perfume 0.60% 0.60% 0.60% 0.60% Perfume microcapsule 0.25% 0.25% 0.25%0.25% Preservative 0.0075%  0.0075%  0.0075%  0.0075%  Structurant 0.11%0.15%  0.2%  0.2% Calcium chloride 0.05% 0.05% 0.05% 0.05% Blue dye0.00028%   0.00028%   0.00028%   0.00028%   Violet, dye 0.00052%  0.00052%   0.00052%   0.00052%   Formic acid 0.025%  0.025%  0.025% 0.025%  Deionized water Balance Balance Balance Balance ¹ Modifiedpolysaccharide according to the invention (e.g., Sample 1 or Sample 2above). ² CAE 10 fatty acid ethoxylate (coconut fatty acid reacted withan average of ten moles of ethylene oxide). ³ 1,2-propanediol. ⁴Vitasyn ® Blue AE 90 dye, available from Clariant International Ltd,Muttenz, Switzerland. ⁵ Sanolin ® Violet dye, available from ClariantInternational Ltd, Muttenz, Switzerland.

TABLE 21 Furniture Polish Compositions INGREDIENTS (Wt %) Formula 1Formula 2 Formula 3 Formula 4 Modified 0.5% 0.5% 0.5% 0.5%polysaccharide ¹ Hydroxyacetic 3.0% 3.0% 3.0% 3.0% acid Limonene ² 5.0%5.0% 5.0% 5.0% (hydrocarbon solvent) Alcohol C12-C15, 3.0% 3.0% 3.0%3.0% ethoxylated ³ Tall oil fatty acid ⁴ 3.2% 3.2% 3.2% 3.2%Polydimethyl- 3.0% 1.5%  0%  0% siloxane fluid ⁵ Carnauba wax ⁶  0%  0% 1%  0% pH 5 5 5 5 Deionized water Balance Balance Balance Balance ¹Modified polysaccharide according to the invention (e.g., Sample 1 orSample 2 above). ² Available from Sigma Aldrich, St. Louis, MissouriUSA. ³ NEODOL ® 25-7, available from Shell Chemicals, Houston, TexasUSA. ⁴ XTOL ® 100 Tall Oil Fatty Acid, available from Georgia-PacificChemicals, Atlanta, Georgia USA. ⁵ XIAMETER ® Polydimethylsiloxane(PDMS) Fluids, available from available from Dow Corning, Midland,Michigan USA. ⁶ Available from the Frank B. Ross Co., Rahway, New JerseyUSA.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1-18. (canceled)
 19. A method of achieving a modified substratecomprising applying to the substrate a surface modifying compositioncomprising: a) from about 0.1 wt % to about 1.0 wt % by weight of thecomposition of a cationically modified and silicone graftedpolysaccharide; b) from about 5 wt % to about 60 wt % by weight of thecomposition of at least one surfactant; and c) a carrier.
 20. The methodof claim 19 wherein the substrate is a keratinaceous surface.
 21. Themethod of claim 19 wherein the substrate is cellulose, wood, ceramic,glass or metallic.